Molecular transport junctions: Current from electronic excitations in the leads

Using a model comprising a 2-level bridge connecting free electron reservoirs we show that coupling of a molecular bridge to electron-hole excitations in the leads can markedly effect the source-drain current through a molecular junction.In some cases, e.g. molecules that exhibit strong charge transfer transitions, the contribution from electron-hole excitations can exceed the Landauer elastic current and dominate the observed conduction.Comment: 4 pages, 2 figures, submitted to PR

Training the Next Generation of Translational Scientists: The Case Western Reserve University Translational Fellows Program

Background: An important part of biomedical research is the translation of discoveries into clinical or community applications that impact patient health. For a vast majority of clinical applications and sustainable community interventions, a time-tested way to get innovations to patients is through licensing of the technology and commercial development, often through startups. While biomedical scientists and trainees are schooled in discovery research, the processes of commercialization are foreign or intimidating. Further, many trainees will not aspire to a faculty position, and other avenues of advancement are desirable. Methods: At Case Western Reserve University, we developed and launched a Translational Fellows Program to provide such training for the community, focusing specifically on graduate students and postdoctoral fellows. The goals of this program include familiarizing our trainees with the principles of entrepreneurship, product development, and startups. This is accomplished through study of their laboratory\u27s technology to identify points of translational focus and to increase awareness to potentially move ideas and products toward societal impact. This program leverages much of our existing infrastructure and provides a mechanism for the prioritization of the translation of the technology as well as release-time to promote effort. Results: Launched in summer 2020, our first cohort had 3 of the 12 fellows launching startups based on their technology and submitting an National Institutes of Health Small Business Innovation Research (SBIR) proposal. At least 80% reported increased knowledge and confidence in five of six key translational competencies. Conclusion: We are now continuing and improving the program and searching for sustainable support to stabilize the program for a long-term productive future

A comparison of spectrophotometric and denuder based approaches for the determination of gaseous molecular iodine

The presence of molecular iodine in the atmosphere is thought to have implications for both climate and human nutritional health, but measurement of the gas at low concentrations requires technically demanding techniques that are not widely accessible. Here, amylose coated denuder tubes and solvent traps coupled with spectrophotometric detection are evaluated and compared as relatively cheap and straightforward methods to measure gaseous molecular iodine at environmentally relevant concentrations. Denuder tubes were found to give unacceptably low and highly variable recoveries of molecular iodine from a test gas source, with values ranging from 1 to 62%. Blank concentrations were also high, being equivalent to a gas phase concentration of 5 pptv under typical operating conditions. Ethanol and hexane solvent traps gave much better performance. Optimisation of the hexane solvent trap method gave 100% recovery and an atmospheric limit of detection of 70 pptv, which is within the range of concentrations observed in the coastal marine atmosphere

Measuring the quantum efficiency of single radiating dipoles using a scanning mirror

Using scanning probe techniques, we show the controlled manipulation of the radiation from single dipoles. In one experiment we study the modification of the fluorescence lifetime of a single molecular dipole in front of a movable silver mirror. A second experiment demonstrates the changing plasmon spectrum of a gold nanoparticle in front of a dielectric mirror. Comparison of our data with theoretical models allows determination of the quantum efficiency of each radiating dipole.Comment: 4 pages, 4 figure

Casimir Force between a Dielectric Sphere and a Wall: A Model for Amplification of Vacuum Fluctuations

The interaction between a polarizable particle and a reflecting wall is examined. A macroscopic approach is adopted in which the averaged force is computed from the Maxwell stress tensor. The particular case of a perfectly reflecting wall and a sphere with a dielectric function given by the Drude model is examined in detail. It is found that the force can be expressed as the sum of a monotonically decaying function of position and of an oscillatory piece. At large separations, the oscillatory piece is the dominant contribution, and is much larger than the Casimir-Polder interaction that arises in the limit that the sphere is a perfect conductor. It is argued that this enhancement of the force can be interpreted in terms of the frequency spectrum of vacuum fluctuations. In the limit of a perfectly conducting sphere, there are cancellations between different parts of the spectrum which no longer occur as completely in the case of a sphere with frequency dependent polarizability. Estimates of the magnitude of the oscillatory component of the force suggest that it may be large enough to be observable.Comment: 18pp, LaTex, 7 figures, uses epsf. Several minor errors corrected, additional comments added in the final two sections, and references update

Intercomparison Methods for Satellite Measurements of Atmospheric Composition: Application to Tropospheric Ozone from TES and OMI

We analyze the theoretical basis of three different methods to validate and intercompare satellite measurements of atmospheric composition, and apply them to tropospheric ozone retrievals from the Tropospheric Emission Spectrometer (TES) and the Ozone Monitoring Instrument (OMI). The first method (in situ method) uses in situ vertical profiles for absolute instrument validation; it is limited by the sparseness of in situ data. The second method (CTM method) uses a chemical transport model (CTM) as an intercomparison platform; it provides a globally complete intercomparison with relatively small noise from model error. The third method (averaging kernel smoothing method) involves smoothing the retrieved profile from one instrument with the averaging kernel matrix of the other; it also provides a global intercomparison but dampens the actual difference between instruments and adds noise from the a priori. We apply the three methods to a full year (2006) of TES and OMI data. Comparison with in situ data from ozonesondes shows mean positive biases of 5.3 parts per billion volume (ppbv) (10%) for TES and 2.8 ppbv (5%) for OMI at 500 hPa. We show that the CTM method (using the GEOS-Chem CTM) closely approximates results from the in situ method while providing global coverage. It reveals that differences between TES and OMI are generally less than 10 ppbv (18%), except at northern mid-latitudes in summer and over tropical continents. The CTM method further allows for CTM evaluation using both satellite observations. We thus find that GEOS-Chem underestimates tropospheric ozone in the tropics due to possible underestimates of biomass burning, soil, and lightning emissions. It overestimates ozone in the northern subtropics and southern mid-latitudes, likely because of excessive stratospheric influx of ozone.Earth and Planetary SciencesEngineering and Applied Science

Size-dependent oscillator strength and quantum efficiency of CdSe quantum dots controlled via the local density of states

We study experimentally time-resolved emission of colloidal CdSe quantum dots in an environment with a controlled local density of states (LDOS). The decay rate is measured versus frequency and as a function of distance to a mirror. We observe a linear relation between the decay rate and the LDOS, allowing us to determine the size-dependent quantum efficiency and oscillator strength. We find that the quantum efficiency decreases with increasing emission energy mostly due to an increase in nonradiative decay. We manage to obtain the oscillator strength of the important class of CdSe quantum dots. The oscillator strength varies weakly with frequency in agreement with behavior of quantum dots in the strong confinement limit. Surprisingly, previously calculated tight-binding results differ by a factor of 5 with the measured absolute values. Results from pseudopotential calculations agree well with the measured radiative rates. Our results are relevant for applications of CdSe quantum dots in spontaneous emission control and cavity quantum electrodynamic

Characterization of soluble bromide measurements and a case study of BrO observations during ARCTAS

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (\u3e2 pmol mol−1) under unpolluted conditions (NOmol−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008

Spontaneous emission of an atom placed near a nanobelt of elliptical cross-section

Spontaneous emission of an atom (molecule) placed near a nanocylinder of elliptical cross-section of an arbitrary composition is studied. The analytical expressions have been obtained for the radiative and nonradiative channels of spontaneous decay and investigated in details.Comment: 35 pages, 11 figure